WO2020193087A1 - Polyéther polyol - Google Patents

Polyéther polyol Download PDF

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Publication number
WO2020193087A1
WO2020193087A1 PCT/EP2020/055552 EP2020055552W WO2020193087A1 WO 2020193087 A1 WO2020193087 A1 WO 2020193087A1 EP 2020055552 W EP2020055552 W EP 2020055552W WO 2020193087 A1 WO2020193087 A1 WO 2020193087A1
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WO
WIPO (PCT)
Prior art keywords
polyether polyol
acid
hydrogen phosphate
group
dihydrogen phosphate
Prior art date
Application number
PCT/EP2020/055552
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English (en)
Inventor
Lies BONAMI
Joris Karel Peter Bosman
Els Elisabeth MERCIER
Original Assignee
Huntsman International Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman International Llc filed Critical Huntsman International Llc
Priority to EP20706552.5A priority Critical patent/EP3947522A1/fr
Priority to BR112021017894A priority patent/BR112021017894A2/pt
Priority to US17/434,781 priority patent/US20220135730A1/en
Priority to CA3130869A priority patent/CA3130869A1/fr
Priority to CN202080023892.0A priority patent/CN113661198A/zh
Priority to MX2021011618A priority patent/MX2021011618A/es
Publication of WO2020193087A1 publication Critical patent/WO2020193087A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a process for providing a homogeneous polyether polyol composition, which process comprises the following steps:
  • Providing a crude polyether polyol mixture which comprises a polyether polyol and a Group IA or Group 11 A metal ion;
  • Methods for preparing polyether polyols typically involve reacting a starting compound having a plurality of active hydrogen atoms with one or more alkylene oxides in the presence of a base catalyst, preferably a strong base, such as potassium hydroxide.
  • a base catalyst preferably a strong base, such as potassium hydroxide.
  • suitable starting compounds are polyfunctional alcohols, typically comprising 2 to 6 hydroxyl groups.
  • examples of such alcohols are glycol, e.g. diethylene glycol, dipropylene glycol, glycerol, di- and polyglycerols, pentaerythritol, trimethylolpropane, diethanolamine, triethanolamine, sorbitol, mannitol, etc.
  • Alkylene oxides commonly used are ethylene oxide, propylene oxide, butylene oxide or mixtures of two or more of these.
  • polyether polyol After neutralisation, several steps are required to provide a polyether polyol, which meets the specifications for further use of the polyether polyol composition, as raw material, in polyurethane (PU) manufacturing (flexible and / or rigid applications).
  • PU polyurethane
  • polyether polyol can be reacted with polyisocyanate compounds, such as methylene diphenyl diisocyanate (MDI) or toluene diisocyanate (TDI).
  • MDI methylene diphenyl diisocyanate
  • TDI toluene diisocyanate
  • One of these processes involves the formation of a salt, which precipitates in the medium, and which is then filtered off, in order to collect the polyether polyol composition in the end of the process.
  • WO 93/19 113 discloses a process, wherein use is made of an inorganic acid, which is present at a concentration, at which the inorganic acid is soluble in the crude polyether polyol mixture and in the salt formed in the polyether polyol composition.
  • this process needs an extraction of a part of the base catalyst before neutralisation, which makes such process complex and not convenient for the user.
  • the colour of the polyether polyol composition will increase over time, in particular when an increase of temperature is applied to the composition. An increase of coloration can be linked to the fact that side reactions occur, which should be avoided.
  • the present invention provides a process as disclosed hereinbefore, characterised in that said strong acid is a pentavalent organic phosphorus compound, and in that said salt is a phosphorus-containing compound based organic salt, which is soluble in said polyether polyol composition.
  • the presence of said phosphorus-containing compound based organic salt does not adversely affect the color of the homogeneous polyether polyol composition over time, which can thereby be used in several applications, e.g. for the manufacturing of polyurethane products.
  • the salt of the present invention has less trimerisation catalytic activity in the polyether polyol composition, when reacted with isocyanate containing compounds and compared with known polyether polyol composition.
  • the present invention provides a process, which is cost-efficient and convenient for the user, who does not need to filter off or remove any salt, for using the polyether polyol composition in an efficient way in several fields of applications.
  • the process is convenient, since it is possible to apply the process of the present invention in one reactor, which is also cost efficient in case of industrial-scale application.
  • said crude polyether polyol mixture comprises a Group IA or Group IIA metal ion up to 4800 ppm, preferably up to 4700 ppm, more preferably up to 4600 ppm, even more preferably up to 4500 ppm.
  • said crude polyether polyol mixture comprises up to 4000 ppm, preferably up to 3800 ppm, more preferably up to 3600 ppm of said Group IA or Group IIA metal ion.
  • said pentavalent organic phosphorus compound is selected from the group consisting of organic phosphoric acid, organic phosphonic acid, organic phosphinic acid, derivatives and mixtures thereof.
  • said pentavalent organic phosphorus compound is selected from the group consisting of mono-alkyl dihydrogen phosphate, dialkyl hydrogen phosphate, alkyl phosphonic acid, alkyl alkyl phosphonic acid, dial kylphosphinic acid, derivatives and combinations thereof.
  • said pentavalent organic phosphorus compound has a high degree of compatibility with a large list of polyether polyol composition (for rigid and / or flexible applications), which is particularly advantageous. In other words, this gives the user the latitude in selecting several types of polyether polyols.
  • said pentavalent organic phosphoric compound is selected from the group consisting of dimethyl hydrogen phosphate, methyl dihydrogen phosphate, diethyl hydrogen phosphate, ethyl dihydrogen phosphate, dipropyl hydrogen phosphate, propyl dihydrogen phosphate, dibutyl hydrogen phosphate, butyl dihydrogen phosphate, dipentyl hydrogen phosphate, pentyl dihydrogen phosphate, dihexyl hydrogen phosphate, hexyl dihydrogen phosphate, diheptyl hydrogen phosphate, heptyl dihydrogen phosphate, dioctyl hydrogen phosphate, octyl dihydrogen phosphate, bis(l-methylheptyl) hydrogen phosphate, 1-methylheptyl dihydrogen diphosphate, bis(2-ethyl-hexyl) hydrogen phosphate, 2- ethyl-hexyl dihydrogen phosphate, didodecyl hydrogen
  • said strong acid has a pKa lower than 5, preferably ranging from 0.05 to 4.5, more preferably from 1.2 to 3.
  • said crude polyether polyol mixture is obtained by reacting a starting compound having at least one active hydrogen atom with at least one alkylene oxide, preferably selected in the group consisting of ethylene oxide, propylene oxide and mixtures thereof, in the presence of a base catalyst.
  • the base catalyst of the present invention can be cesium hydroxide, potassium hydroxide, sodium hydroxide or any other equivalent compound, based on Group IA or Group IIA metal ion.
  • said starting compound comprises 1 to 8 hydroxyl groups or primary / secondary amine groups.
  • said starting compound comprises at least one functional alcohol, preferably monofunctional alcohol or polyfunctional alcohol, which comprises 1 to 8 hydroxyl groups.
  • said starting compound is selected from the group consisting of diethylene glycol, propylene glycol, dipropylene glycol, glycerol, diglycerol, polyglycerols, pentaerythritol, trimethylolpropane, diethanolamine, triethanolamine, sorbitol, mannitol, sucrose, ethylene diamine, oligomeric diphenyl methane diamine, toluene diamine, Mannich bases, and mixtures thereof.
  • the present invention also relates to a homogeneous polyether polyol composition made of polyether polyol and a phosphorus-containing compound based organic salt, which is, preferably completely, soluble in said polyether polyol composition.
  • the process of the present invention comprises a dehydration step after neutralisation, in order to provide a dried polyether polyol composition.
  • the water content in the polyether polyol can preferably be lower than 2 wt %, more preferably lower than 1 wt %, even more preferably lower than 0.1 wt %, based on the total weight of the polyether polyol composition.
  • the present invention concerns a reaction mixture comprising at least one homogeneous polyether polyol composition obtained according to the present invention and at least one isocyanate containing compound.
  • the present invention also relates to polyurethane product obtained by reacting the components of the reaction mixture of the present invention.
  • a foam can be obtained by reacting the components of a reaction mixture according to the present invention and by curing said reaction mixture for manufacturing the foam.
  • the homogeneous polyether polyol composition of the present invention can be used in foams, coatings, adhesives, elastomers and resins.
  • the polyether polyol composition of the present invention is suitable for manufacturing polyurethane foams, in particular flexible or rigid foams.
  • the present invention concerns a homogeneous polyether polyol composition obtained by applying the following steps:
  • said homogeneous polyether polyol composition characterised in that said strong acid is a pentavalent organic phosphorus compound, and in that said salt is a phosphorus-containing compound based organic salt, which is soluble in said homogeneous polyether polyol composition.
  • said crude polyether polyol mixture comprises a Group IA or Group IIA metal ion up to 4800 ppm, preferably up to 4700 ppm, more preferably up to 4600 ppm, even more preferably up to 4500 ppm.
  • said strong acid has a pKa lower than 5, preferably ranging from 0.05 to 4.5, more preferably from 1.2 to 3.
  • said pentavalent organic phosphorus compound is selected from the group consisting of organic phosphoric acid, organic phosphonic acid, organic phosphinic acid, derivatives and mixtures thereof.
  • said pentavalent organic phosphorus compound is selected from the group consisting of mono-alkyl dihydrogen phosphate, dialkyl hydrogen phosphate, alkyl phosphonic acid, alkyl alkyl phosphonic acid, dialkylphosphinic acid, derivatives and combinations thereof.
  • soluble used in the present invention should be understood as meaning that the salt formed in the process after neutralisation is dissolved in the polyether polyol composition of the present invention. This solubility is visually observed by the fact that the salt does not precipitate in the polyether polyol composition. This results in a homogeneous polyether polyol composition, one single phase composition.
  • polyether polyol composition should be understood as meaning that the substance(s), referred hereinafter as the salt or the strong acid of the present invention will remain in the polyether polyol composition over time (no precipitation or hazy solution).
  • phosphorus-containing compound based organic salt refers to the salt formed when the process of the present invention is applied. This salt results from the type of metal ion present in the crude polyether polyol mixture and the type of acid used for neutralisation. Since the acid, is a pentavalent organic phosphorus compound, the resulted organic salt comprises phosphorus atom.
  • the strong acid can be added to the crude polyether polyol mixture as an aqueous acid solution.
  • an excess amount of acid can be used for neutralisation, in order to provide polyether polyol composition, which is stable over time (storage). Complete neutralisation of the crude polyether polyol mixture is guaranteed.
  • the reaction between alkylene oxides and alcohol groups during the polymerization of the polyether polyol is typically performed in the presence of a base catalyst such as an alkali metal hydroxide, e.g. sodium hydroxide, potassium hydroxide or cesium hydroxide, or mixtures thereof, whereas most preferably potassium hydroxide is used.
  • a base catalyst such as an alkali metal hydroxide, e.g. sodium hydroxide, potassium hydroxide or cesium hydroxide, or mixtures thereof, whereas most preferably potassium hydroxide is used.
  • the amount of catalyst used to provide the crude polyether polyol mixture can be in the range of 0.05 to 2 wt %, preferably 0.05 - 1 wt %, more preferably in the range of 0.10 to 0.5 wt %, and most preferred in the range of 0.13 to 0.40 wt %, based on the total weight of the polyether polyol to be prepared in the crude polyether polyol mixture during polymerization reaction.
  • the crude polyether polyol mixture is provided by catalytically polymerizing a starting compound with alkylene oxides (also referred to as epoxides).
  • Suitable starting compounds can have 1 to 8 hydroxyl group(s). Examples of such alcohols are glycols, e.g.
  • MDA diaminodiphenyl- methane
  • alkylene oxides used are typically ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or mixtures of two or more of these.
  • the polyether polyol comprising more than one type of alkylene oxide may be a so-called block polyether comprising at least two different alkylene oxides, obtained e.g. by reacting the starting compound with one of the alkylene oxide components. After termination of this polyaddition reaction, the intermediate polyether polyol is reacted with any other of the alkylene oxides. This sequential addition of blocks of alkylene oxides can be repeated. As such blocks of different alkylene oxides are added to the polyether polyol.
  • the polyether polyol comprising more than one type of alkylene oxide may be a so-called random polyether comprising at least two different alkylene oxides, obtained e.g. by reacting the starting compound with a combination of at least two different alkylene oxide components. After termination of this polyaddition reaction, the different alkylene oxides will be at random in the sequences of the polyether chains.
  • the polyether polyols may be provided to the polyether polyols.
  • polyols with an EO content up to 100 % can be used, most preferably, the polyether polyol comprises less than 80 % EO, an EO content of 5 to 80 % EO, and most preferred an EO content in the range of 5 to 35 % such as in the range of 10 to 30 %.
  • the EO content is the number of EO-monomers in the polyol over the total of alkyloxide monomers in the polyol, expressed as a percentage.
  • polyol with an EO content of about 0 wt % or equal to 0 wt % is also advantageously used.
  • EO may be present at random or as blocks and are preferably combined with PO in the polyether polyol.
  • the polyether polyol is a combined EO-PO polyether polyol, meaning that the polyether polyol is provided by reacting the starting component with alkylene oxides selected from EO and PO only, and this at random or in sequences to provide block polymers.
  • the polyether polyols may be EO or PO tipped, which means that at least the last alkylene oxide added to the polyol is an EO or PO respectively.
  • the EO content of the polyether polyol may be in the range of 0 to 80 wt %.
  • the Group IA or Group IIA metal ion is selected from the group consisting of potassium, sodium, cesium, barium, and mixtures thereof.
  • Neutralisation step can be performed by adding a strong acid to said crude polyether polyol mixture.
  • the excess of acid is determined by the specification of acidity of the polyether polyol, this is expressed in mg KOH/g.
  • the specifications are 0.01-0.1 mg KOH/g.
  • an equivalent of 0.05 mg KOH/g extra is added to the polyether polyol.
  • the strong acid of the present invention is selected from the group consisting of mono-alkyl dihydrogen phosphate, dialkyl hydrogen phosphate, alkyl phosphonic acid, alkyl alkyl phosphonic acid, dial kyl phosphinic acid, derivatives and combinations thereof.
  • dialkyl phosphinic acid has the following formula (I):
  • R1 and R2 are preferably the same or different and are each C1-C26 alkyl, C2-C18-alkenyl, C6-C18-aryl, C7-C18-alkylaryl.
  • R1 and R2 are the same or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, benzyl, phenyl, octyl, n- octyl, iso-octyl, hepyl, n-heptyl, iso-heptyl, and combinations thereof.
  • alkyl phosphonic acid has the following formula (II):
  • R3 is preferably selected from the group consisting of C1-C26 alkyl, C2-C18-alkenyl, C6-C18-aryl, C7-C18-alkylaryl.
  • R3 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, benzyl, phenyl, octyl, n-octyl, iso-octyl, hepyl, n-heptyl, iso-heptyl, and combinations thereof.
  • said strong acid alkyl alkyl phosphonic acid has the following formula (III):
  • R3 and R4 are the same or different and are each C1-C26 alkyl, C2-C18-alkenyl, C6-C18-aryl, C7-C18-alkylaryl.
  • R3 and R4 are the same or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl, isohexyl benzyl, phenyl, octyl, n- octyl, iso-octyl, hepyl, n-heptyl, iso-heptyl, and combinations thereof.
  • the strong acid is selected from the group consisting of mono-alkyl dihydrogen phosphate, dialkyl hydrogen phosphate, derivatives and mixtures thereof.
  • the strong acid has advantageously the following formula (III): O-H
  • R5 and R6 are the same or different and are each C1-C26 alkyl, C2-C18-alkenyl, C6-C18-aryl, C7-C18-alkylaryl, or hydrogen.
  • R5 and R6 are the same or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl, isohexyl benzyl, phenyl, octyl, n- octyl, iso-octyl, hepyl, n-heptyl, iso-heptyl, and combinations thereof.
  • the neutralisation step enables forming the neutralised polyether polyol composition.
  • the neutralisation preferably consists in a complete neutralisation of the crude polyether polyol mixture.
  • an aqueous acid solution may be used to neutralize the crude polyether polyol mixture.
  • the base catalyst can be for instance NaOH or KOH
  • the strong acid can be dibutyl hydrogen phosphate.
  • Neutralisation step can be performed by adding for instance between 1.00 to 1.1 moles of dibutyl hydrogen phosphate for each mole of KOH or NaOH.
  • one embodiment consists in applying a temperature between 25 to 160°C, preferably between 50 to 150°C to the crude polyether polyol mixture. This temperature can be kept for a certain time, from 0.5 to 10 hours, preferably up to 7 hours, more preferably up to 6 hours, during or after neutralisation.
  • the resulting polyether polyol composition comprises polyether polyol of the present invention along with an organic salt.
  • the latter is formed by the reaction occurring between Group IA or Group I IA metal containing base catalyst and said strong acid, providing a neutralized polyether polyol mixture, optionally removing at least part of the water from the neutralized polyether polyol mixture.
  • polyether polyol composition is obtained, wherein said organic salt is completely soluble in the composition.
  • the polyether polyol composition is dried (dehydration step).
  • the present invention provides a homogeneous polyether polyol composition, which is ready to be used, e.g., in manufacturing polyurethane products.
  • the complete dissolution of the salt is visually assessed in the end of the process.
  • Polvether polyol A is a glycerol started EO/PO polyether polyol with an OH value of 43 mg KOH/g and an EO-content of 74.7 wt %.
  • Polvether polyol C is a dipropylene glycol started EO/PO polyether polyol with an OH value of 43 mg KOH/g and an EO-content of 16 wt %.
  • Polvether polyol F is a sucrose-diethylene glycol started PO polyether polyol with an OH value of 440 mg KOH/g.
  • the OH value (also referred as OH number or OH content) can be measured according to ASTM D1957 standard and is expressed in mg KOH/g.
  • OH value can also be determined by reacting the hydroxyl groups with an acid anhydride and titrating the acid liberated with potassium hydroxide solution.
  • the unit for OH value is expressed in mg KOH/g polyol.
  • OHv (56.1 g/mol KOH x polyol functionality xlOOO)/ (molecular weight).
  • the amount of K + in the crude polyether polyol can be determined by atomic absorption spectroscopy. Alternatively, this amount can be determined by calculating the amount of KOH added to the mixture.
  • Dehydration of the polyether polyol composition is performed at reduced pressure lOmbar, while increasing the temperature stepwise to 120°C.
  • example 1 is reproduced, except that use is made of other types of strong acids, as illustrated in Table 1.
  • Table 1 shows the amounts of strong acids used to perform the neutralisation.
  • the amount of K + in the crude polyether polyol mixture is equal to 1812ppm.
  • Dehydration of the polyether polyol composition is performed at lOmbar and by increasing the temperature stepwise to 120°C.
  • Table 2 illustrates the types and amounts of strong acids used to neutralise the crude polyether polyol mixture, as recited hereinabove, and the results when the polyether polyol composition is obtained.
  • Example 1 is reproduced with the addition of 0.74 g of KOH (36 wt % KOH solution in water) in the presence of an inorganic acid.
  • KOH 36 wt % KOH solution in water
  • the obtained crude polyether polyol mixture is heated to 90°C under nitrogen atmosphere.
  • 1.21 g of a 20 wt % H3PO4 solution was added and stirred for 30 min at 90°, until complete neutralisation is reached.
  • the neutralized polyether polyol composition is cooled down to room temperature.
  • the amount of K + in the crude polyether polyol mixture is equal to 1874ppm.
  • Table 3 shows the results when H3PO4 solution is used, as well as other types of acids are used.
  • white salt precipitates and/or the polyether polyol compositions are not homogeneous and are haziness solutions.
  • Example 1 is reproduced with 99 g of polyether polyol C mixed with 0.71 g of 36 wt % of KOH solution. 99.71 g of the obtained crude polyether polyol mixture is heated to 90°C under nitrogen atmosphere.
  • the amount of K + in the crude polyether polyol mixture is equal to 2158 ppm.
  • a foam composition is obtained by mixing the components mentioned hereinbelow.
  • a first polyol formulation is provided by using at least one polyether polyol obtained according to the present invention (polyether polyol/water/PO, OH value of 510 and functionality of 5.5) in the presence of a flame retardant, and a catalyst.
  • the polyether polyol composition has been obtained by using dibutyl hydrogen phosphate according to the process of the present invention.
  • the formulation is then foamed in the presence of a blowing agent and Suprasec ® 5025 polymeric MDI (Huntsman).
  • Another formulation is obtained, by using acetic acid to provide a second polyether polyol composition.
  • the properties of the obtained foams are summarized in table 4 hereinbelow.
  • Cream time refers to the time required for the reaction mixture to change from the liquid state to a creamy state and starts to foam (expand) subsequently.
  • String time is time from mixing to the instant at which it is possible to pull a string of polymer from the reacting mixture using a spatula.
  • Free rise density refers to density measured on foam samples made under atmospheric conditions (in the presence of blowing agents) according to ISO 845 or DIN 4102.
  • an isocyanate group means one isocyanate group or more than one isocyanate group.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé d'obtention d'une composition de polyéther polyol homogène, comprenant les étapes suivantes consistant à : fournir un mélange de polyéther polyol brut comprenant un polyéther polyol et un ion métallique du groupe IA ou du groupe IIA ; neutraliser ledit mélange de polyéther polyol brut par ajout d'un acide fort audit mélange, ce qui permet d'obtenir une composition de polyéther polyol neutralisé, qui comprend ledit polyéther polyol conjointement avec un sel dudit ion de métal du groupe IA ou du groupe IIA et dudit acide fort ; fournir ladite composition de polyéther polyol homogène, caractérisé en ce que ledit acide fort est un composé de phosphore organique pentavalent, et en ce que ledit sel est un sel organique à base de composé contenant du phosphore, qui est soluble dans ladite composition de polyéther polyol.
PCT/EP2020/055552 2019-03-25 2020-03-03 Polyéther polyol WO2020193087A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP20706552.5A EP3947522A1 (fr) 2019-03-25 2020-03-03 Polyéther polyol
BR112021017894A BR112021017894A2 (pt) 2019-03-25 2020-03-03 Processo para prover uma composição de poliéter poliol homogênea, composição de poliéter poliol homogênea, mistura de reação, e, produtos de poliuretano
US17/434,781 US20220135730A1 (en) 2019-03-25 2020-03-03 Polyether polyol
CA3130869A CA3130869A1 (fr) 2019-03-25 2020-03-03 Polyether polyol
CN202080023892.0A CN113661198A (zh) 2019-03-25 2020-03-03 聚醚多元醇
MX2021011618A MX2021011618A (es) 2019-03-25 2020-03-03 Polieter poliol.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19164934 2019-03-25
EP19164934.2 2019-03-25

Publications (1)

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WO2020193087A1 true WO2020193087A1 (fr) 2020-10-01

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US (1) US20220135730A1 (fr)
EP (1) EP3947522A1 (fr)
CN (1) CN113661198A (fr)
AR (1) AR118487A1 (fr)
BR (1) BR112021017894A2 (fr)
CA (1) CA3130869A1 (fr)
MX (1) MX2021011618A (fr)
WO (1) WO2020193087A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1083939A (en) * 1964-12-24 1967-09-20 Kalk Chemische Fabrik Gmbh Production of self-extinguishing polyurethanes
US4521548A (en) * 1983-04-12 1985-06-04 The Dow Chemical Company Preparation of polyether polyols
WO1993019113A1 (fr) 1992-03-24 1993-09-30 The Dow Chemical Company Nouveau procede de finissage de polyethers hydroxy-fonctionnels
WO2016100691A1 (fr) * 2014-12-19 2016-06-23 3M Innovative Properties Company Additif, compositions et procédés de traitement à base de polymère de poly(oxyalkylène)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732367A (en) * 1956-01-24 ruuivj
US5472987A (en) * 1991-06-25 1995-12-05 Osi Specialties, Inc. Surfactant composition for flexible polyurethane foam
US6471905B1 (en) * 1997-09-29 2002-10-29 Bayer Aktiengesellschaft Internal release agents for producing polyurethane moulded bodies
KR100990062B1 (ko) * 2003-01-28 2010-10-29 아사히 가라스 가부시키가이샤 폴리에테르폴리올 조성물 및 그 용도
US7005552B2 (en) * 2003-11-03 2006-02-28 Bayer Materialscience Llc Single reactor synthesis of KOH-capped polyols based on DMC-synthesized intermediates
JP2010006964A (ja) * 2008-06-27 2010-01-14 Lion Corp アルキレンオキシド付加物の製造方法
EP2475700B2 (fr) * 2009-09-07 2022-12-21 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'une mousse polyuréthane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1083939A (en) * 1964-12-24 1967-09-20 Kalk Chemische Fabrik Gmbh Production of self-extinguishing polyurethanes
US4521548A (en) * 1983-04-12 1985-06-04 The Dow Chemical Company Preparation of polyether polyols
WO1993019113A1 (fr) 1992-03-24 1993-09-30 The Dow Chemical Company Nouveau procede de finissage de polyethers hydroxy-fonctionnels
WO2016100691A1 (fr) * 2014-12-19 2016-06-23 3M Innovative Properties Company Additif, compositions et procédés de traitement à base de polymère de poly(oxyalkylène)

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AR118487A1 (es) 2021-10-06
US20220135730A1 (en) 2022-05-05
CN113661198A (zh) 2021-11-16
BR112021017894A2 (pt) 2021-12-07
MX2021011618A (es) 2021-10-13
CA3130869A1 (fr) 2020-10-01
EP3947522A1 (fr) 2022-02-09

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